High resolution spectra of H2O2, recorded by means of Fourier transform spectroscopy between 30 and 460 cm1, have been analyzed leading to the determination of the rotational levels of the torsional states (n,τ) for n=0,1,2,3. In order to reproduce these energy levels, Watson type Hamiltonians have been used and it has been possible to observe a staggering of the levels with n=2 and 3 caused by the cis barrier. The torsional band centers have then been fitted using a torsional Hamiltonian of the form {Bγγ,J2γ} +V(γ) with the potential function V(γ) written as V(γ)=V1 cos 2γ+V2 cos 4γ+V3 cos 6γ+V4 cos 8γ where the torsional coordinate 2γ is the dihedral angle defining the relative position of the two O–H bonds. The potential constants in cm1 are V1=1036.97±23.1 cm1, V2=657.53±5.2 cm1, V3=50.89±3.3 cm1, V4=2.524±0.83 cm1 which correspond to barrier heights Vtrans =387.07±0.20 cm1, Vcis =2562.8±60 cm1, and to a potential minimum located at 2γ=111.9°±0.4° from the cis configuration. It is also shown that the rotational constants derived from the fit to the experimental rotational levels cannot be reproduced using a model which does not take into account vibrational corrections.

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See AIP document no. PAPS JCPSA-91-1504-18for 18 pages of H2O2 torsion‐rotation levels.
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